200522122 九、發明說明： 【發明所屬之技術領域】 本發明係關於放出電子之鑽石電子放出元件及使用該鑽 石電子放出元件之電子線源，其廣泛地運用於高頻放大、 微波振盪、發元元件、電子線曝光裝置等。 【先前技術】 近年來，除了熱陰極之外，使用鉬或碳奈米管等製成 冷陰極元件的開發也在進行中。又，鑽石陰極由於有負的 電子親和力，因此也受到注意。 有各種形態的鑽石陰極曾被發表過。例如，有在例如 W093/15522號公報所揭示之pn型接合或J〇urnal 〇f Vac仙瓜 Science and Technology B14(1996)2050所揭示的金屬陰極 上塗布鑽石者。如圖8所示，pn型接合係在p型鑽石82上， 積層η型鑽石81，在其上形成電極80，加上偏壓，而放出 電子。又，亦有人提出如日本專利公報特開平8_264111號 或W098/44529公報所揭示之在Si的鑄模中形成鑽石，而形 成尖銳化的鑽石陰極者。 上述鑽石陰極係利用強電場將電子放出到真空中者，但 也可以用光激發電子，再從陰極放出電子。例如，日本專 利公報特開平10-149761號、特開平、特開 2000-357449號即提出此等技術。此等均係測量所放出之 電子而做為光檢出器使用者。 【發明内容】 上述專利文獻所揭示的元件都須施加強電場或高操作 96090.doc 200522122 子從元件放射火到真空中。而做 人所注―冷陰極中…加強電場，藉由在： 多=的射極上設置電極，而降低操作電堡，但若要進: :提高動作效率及降低驅動電力，則要求更低的電磨動 提供更小型、操 使用其之電子線 本發明之目的即在於解決上述問題， 作電壓更低、高效率的電子放射元件及 源0 -本I月之鑽石電子放出元件具有對陰極照射光之發光 元件，且陰極的至少電子放出面係由鑽石所構成。如圖4 所不’由於其具有發光元件，可藉由光將電子激發到比真 空能階25為高的鑽石的導帶21以上，故可大幅降低放出電 子的電壓，而可得到可低電壓驅動的小型電子放出元件。 上述陰極之電子放出面較佳為口型鑽石半導體。η型鑽 石之雜質能階接近傳導帶，故即使被能量較低的光所激 發，亦能將電子激發到傳導帶’進而放出電子，故效率較 佳。 上▲述發光7L件較佳由鑽石所構成。鑽石之帶隙加nd gap)較大’可用較高能量激發電子，故可提高動作效率。 上述陰極之電子放出面亦可為？型鑽石半導體。鑽石的 表面上即使產生能帶（band)的彎曲，ρ型鑽石半導體由於在 表面附近的電位降低，故被激發到傳導帶的電子容易被放 出。此時P型鑽石半導體中較佳含有結晶缺陷或邮成分。 所謂結晶缺陷是晶袼空位缺陷、雜質、晶格空位對造成之 96090.doc 200522122 缺陷、差排缺陷、粒界、雙晶等。又，所謂sp2成分，係 指石墨、不定形碳、富勒烯（fullerene)等。 鑽石發光元件除了可以發出如自由激發子發光等的能 量高的光以外，亦可發出例如能帶A等的能量低的光。若 含有結晶缺陷或sP2成分，則鑽石中的帶隙中的能階會增 加，故能量較低的光可用於將電子激發到傳導帶，故可增 加電子放出量。 上述陰極的電子放出面最佳為經氳終端（hydr〇gen terminal)處理者。若經氫終端處理，則做為電子放出面之 鑽石表面之電子親和力為負，故被激發到傳導帶的電子容 易放出到真空中。 又，上述陰極的電子放出面亦可經氧終端（〇xygen termmal)處理。特別是陰極的電子放出面為n型鑽石半導 體時，若其表面經氫終端處理，則表面所產生的電洞會使 做為陰極的載子的電子減少，故陰極為成為高電阻。若表 面經氧終端處理，則不會產生這種現象，故可形成低電阻 的陰極。 再者，上述發元元件較佳係由鑽石的叩接合而成。由 鑽石的ρη接合而成的的發光元件由於會發出自由激發子的 5·27 eV的光等波長較短的光，故容易放出電子。又，藉由 使用與陰極同材料的鑽石，亦易於使發光元件與陰極一體 形成。 又，上述發光元件亦可為鑽石與金屬的肖特基 (Schottky)接合或 MIS(Metal Insulat〇r Semic〇nduct〇r)構造 96090.doc 200522122 所形成者。肖特基揍合或MIS構造的發光其波長較短，故 可以激發較深能階的電子，激發後的電子的能量較高，故 電子放出機率較高，容易放出電子。 上述陰極的電子放出面較佳有尖銳的突出部。電場會 集-中在尖銳的突出部的前端，故可降低操作電壓。 上述發光元件所出的光的波長能量較佳包含5 〇〜54 。 該波長主要是由鑽石的自由激發子所造成。若使用該波 長，則可將電子從較低能階激發到傳導帶，故可藉由例如 從P型雜質之硼之能階激發，以高效率放出電子。 又，上述發光元件所發出之光之波長能量較佳為2 () ev 以上。2·0 eV以上的波長中有起因於鑽石的缺陷等者，例 如能帶A，若光的波長在2·〇 eV以上，則可激發傳導帶附 近的能階，例如摻雜n型氮之鑽石之雜質能階，故可使11型 鑽石陰極以高效率放出電子。先前技術的光電陰極係用較 帶隙大的能量之光激發價電子帶的電子，而本發明如上所 述可用較鑽石的帶隙為小的能量的光激發。如此，發光元 素之光較佳為將鑽石的雜質能階的電子激發到傳導帶者。 又’發光元件之光較佳為將鑽石的帶隙中的能階的電 子激杳到傳導▼者。特別是陰極為ρ型鑽石時，發元元件 之光較佳為將Ρ型鑽石中的石墨、不定形碳、似鑽石碳、 s勒烯、晶格缺陷、差排缺陷、粒界缺陷等任一者所造成 的能階的電子激發到傳導帶者。若以該激發為電子線源， 則即使疋此里較鑽石的能隙小的波長的光，亦可激發到傳 導帶，而可增加電子放出量。 96090.doc 200522122 入，鑽石的情形下， 至少一種亓| 、叙佳匕3氦、磷、硫、鋰之 質。若使用此等雜所目， 素叫包含蝴做為雜 元件中可激π*: 增加载子電子，故可增加發光 中了料之電子，心增加電子放出量。 又，上述發光元件不限於 等III-V族半導體。— πτ用虱化物+導體 千導體。例如可用GaN、趟 CBN的帶隙寬遠6 3 v 以寺特別疋 • 6 ，故發光之能量高，且結晶構造接 近鑽石，故適於形忐g將石 、口日日稱仏接 、/成，、貝猫晶（hetroepitaxy)等積層構造。 由二二述發光元件較佳為與上述陰極-體形成者。藉 :’可縮短電子放出面與發光元件的距離，故可 •電:=損’而提高光電變換效率，且可以將使用該 做=放出元件的電子線源小型化。特別是若使用鑽石 為电先7"件’可容易地將陰極與發光元件-體化。 再者，本發明又提供一種使用鑽石電子放出元件的電 子線源’其特徵為將光照射到陰極的發光元件、及至少其 電子放出面為鑽石的陰極均配置在電子搶的内部。藉由此 構成，可以得到可低電壓驅動的小型電子線源。 又，本發明的電子線源較佳為設置上述至少其電子放 出面為鑽石的陰極’且隔著一空間設置陽極’並將對陰極 為正的電壓施加到陽極而動作者。 再者，上述陰極與陽極之間亦可設置用於控制上述陰極 的放出電子電流的控制電極。使用控制電極可以自由地控 制放出電子的量。 【實施方式】 96090.doc -10- 200522122 實施例1 接著在η型硫摻雜鑽石用減鍍法形成厚！ _的娜。用 微縮影法及濕式餘刻法將A1膜加工成直徑5 _點狀。其 後用RIE法㈣硫摻雜鑽石，如圖1所示將硫摻雜鑽石⑽ 成突起狀。接著在大氣中彻。c下退火3G分鐘，藉以對硫 在而溫高塵法所合成•型鑽石單晶的⑽）面上，用微 波電漿CVD法合成n型硫摻雜鑽石。合成條件為·· P型鑽石 溫度為⑽’甲以氫濃度比為1G%，硫化氫心濃度比 為WOO ppm。n型硫摻雜鑽石的厚度合成到1〇 ^爪。 摻雜鑽石的表面進行氧終端處理。 接著在硫摻雜鑽石丨的平面部、及與形成p型鑽石2的硫 摻雜鑽石的面相反侧的面上，形成電極5、6。形成方法為 在形成電極的鑽石的面上，注入Ar離子，使鑽石石墨化之 後，邊加熱到3001，邊蒸鍍Ti/Au，形成歐姆電極5、6。 將已形成該電極且具有突起部的鑽石置入真空室（未圖 示）内’再將陽極7配置於從突起部前端起隔i 〇〇 μηι處。 首先，在電極5及陽極7之間逐漸施加電壓，從丨kv 起，從η型鑽石的突起部檢測到電子的放出。接著在電極5 及6之間施加1〇 ν的電壓，則從ρη接合層可確認到發光 hv。該發光之波長範圍相當寬，但主波長為235 nm的自由 激發子發光及以430 nm為中心的能帶A的發光。 接著使ρη接合層繼續發光，同時在電極5及7之間逐漸 施加電壓，則從650 V起可以檢測到電子的放出。如此， 可確認出：隨著發光，開始放出電子的電壓會降低。 96090.doc -11 - 200522122 從圖2可得知，位於η型擔χ ; 尘鑽石1的雜質能階23的電子，隨 著發光hv，被激發到比真空能 白5為咼的傳導帶21，而電 子開始放出的臨限值電壓大幅 ^ θ & 又’此蚪在％極檢測 出的電子放出電流增加。 實施例2 在高溫高壓法所合成㈣型鑽石單晶ig的（ιιι)面上， 用微波電漿CVD法合成n型磷摻雜鑽石i 4成條件為：化 型鑽石溫度為870°C ’甲院/氫濃度比為〇 〇5%，麟/甲烧濃 度比W_0Ppm。n型璘摻雜鑽石的厚度合成到ι〇㈣。/ 在η型鑽石上，用相同的微波電漿CVD法合成ρ型硼摻 雜鑽石。合成條件為：Ib型鑽石溫度為83〇它，甲烷/氫濃 度比為6.0%，二職/甲烧濃度比為167 ppm〇p型硼換^ 鑽石的厚度合成到丨〇 μιη。又，p型硼摻雜鑽石中有許多雙 晶等結晶缺陷。 接著與實施例1相同地在P型鑽石上形成點狀的A1膜， 用RIE法蝕刻p型鑽石，如圖3所示將p型鑽石2加工成具有 突起部的形狀。接著再置入微波電漿Cvd裝置中，在85〇 °C下進行10分鐘的氳電漿處理，藉以p型鑽石的表面進行 氫終端處理。再與實施例丨相同地用用Ti/Au形成歐姆電極 5 λ 6 ° 接著與實施例1相同地在真空室設置離1〇〇 μηι的陽極 7 °與實施例1相同地，在電極5及陽極7之間逐漸施加電 壓’從1.5 kV起，從ρ型鑽石的突起部檢測到電子的放 出。接著在電極5及6之間施加10 V的電壓，則從沖接合層 96090.doc -12 - 200522122 可確認到發級。該發光之波長範圍相當寬，但主波長為 235 _的自由激發子發光及以43Gnm為中心廣泛分布的能 帶A的發光。 接著使pn接合層繼續發光，同時在電極5及7之間逐漸 施加電塵，則從_ V起可以檢測到電子的放出。如此， 可確認出：隨著發光，開始放出電子的電壓會降低。 從圖4可得知’位於p型鑽石2的雜質能階“及起因於缺 陷的能階26的電子，被激發到比真空能_為高的傳導帶 2 1 ’而電子開始放出的臨限值電|大幅降低。又，此時在 陽極檢測出的電子放出電流增加。 實施例3 在高溫高壓法所合成的几型鑽石單晶1〇的（1〇〇)面上， 用微波電漿CVD法合成㈣㈣雜鑽石i。合成條件為··化 型鑽石溫度為830°C，甲烷/氫濃度比為6 〇%，二硼烷/甲烷 濃度比為167Ppm。p型硼摻雜鑽石的厚度合成到i〇 接著與實施例1相同地在？型鑽石i上形成點狀的ai膜， 用RIE法蝕刻p型鑽石，如圖5所示將p型鑽石加工成具有突 起邛的形狀。接著再與實施例“目同地用Ti/Au形成歐姆電 極5。再在突起部的周邊蒸鍍W，形成肖特基電極4。再在 硼摻雜鑽石的外周部蒸鍍Si〇2所構成的絕緣體9及M〇，形 成控制電極8。 接著與實施例1相同地在真空室設置離1〇〇 μηι的陽極 7與實施例1相同地，在電極5及陽極7以及電極5與8之 間逐漸施加電壓，分別從1 kV、300 V的電壓起，從ρ型鑽 96090.doc -13- 200522122 石的突起部檢測到電子的放出。接著在電極5及4之間施加 10 V的電壓，則從肖特基接合層可確認到發光hv。該發光 之波長包含從自由激發子發光到能帶A發光的廣泛範圍。 接著使宵特基接合層繼續發光，同時在電極5及7之間 逐漸施加電壓，則從600 V起可以檢測到電子的放出。如 此’可確認出：隨著發光，位於p型鑽石的雜質能階的電 子，被激發到比真空能階為高的傳導帶，而電子開始放出 的臨限值電壓大幅降低。又，此時在陽極檢測出的電子放 出電流增加。 又，若改變於電極5及8之間所施加的電壓，則電子放 出電流呈直線比例變化。再者，即使改變電極5及4之間施 加的電壓而改變發光量，電子放出電流亦發光量呈比例地 增加。 實施例4 與實施例3相同地，在ib型鑽石單晶1〇的（1〇〇)面上，合 成厚ίο μιη的p型硼摻雜鑽石2。如圖6所示，將p型鑽石加 工成具有突起部的形狀。再與實施例2相同地對ρ型鑽石的 表面進行氫終端處理後，用Ti/Au形成歐姆電極5。 另外準備用硼摻雜鑽石及硼摻雜鑽所構成的pn接合的 鑽 D在真空至内5又置遠鑽石LED 60及陽極7。鐵石 LED設置於上述p型鑽石的突起部周邊，陽極設置於從該 突起部先端起離100 μιη的位置。 與實施例1相同地，在電極5及陽極7之間逐漸施加電 壓，分別從丨kV的電壓起，從ρ型鑽石的突起部檢測到電 96090.doc -14- 200522122 子的放出。接著在鑽石LED上施加30 V的電壓使之發光。 該發光中係由數種發光產生，主要之發光是自由激發子發 光，副能帶是能帶A的發光。接著使LED繼續發光，同時 在電極5及陽極6之間逐漸施加電壓，則從650 V起可以檢 測到電子的放出，可確認出電子開始放出的臨限值電壓降 低0 圖7所示為鑽石的能帶圖。圖中的21是傳導帶，22是價 電子帶。藉由5·27 eV的自由激發子發光，位於p型鑽石的 雜質能階24的電子被激發到較真空能階25為高的傳導帶， 經氫終端處理的表面具有負性電子親和力，故容易放出電 子。若改變LED的發光量，則電子放出電流會呈直線比例 變化。 實施例5 用鑽石粉對矽晶圓進行損傷處理後，用燈絲 CVD(filament CVD)法合成p型硼摻雜鑽石。合成條件為： 矽晶圓溫度為800°C，燈絲溫度為21〇〇°c，壓力為13 3 kpa， 曱烷/氫濃度比為2.0%，在溶解於丙酮之硼酸三曱酯中通 入氬氣泡，使硼/碳濃度比成為〇·1%。將？型删摻雜鑽石的 厚度合成到20 μηι。該ρ型鑽石除了具有？型導電性之外’ 由於是多結晶，故包含結晶粒界及差排等缺陷。 接著研磨!>型硼摻雜鑽石的表面，與實施例"目同地米 成點狀的繼，狀職_之，將㈣㈣雜鑽石加工成 突起形狀。再將之放入燈絲CVD裝置中，在85〇它下— 10分鐘的氫電漿處理，對p型鑽石的 订 •鑽石的表面進行氫終端處 96090.doc 15 200522122 理。再與實施例1相同地用Ti/AUB成歐姆電極。 如圖6所示，與實施例4相同地另外準備卯接合的鑽石 LED，在真空室内設置該鑽石LED 6〇及陽極7之外，並設 置突起形狀的p型鑽石2。鑽石LED設置於上述p型鑽石的 突起部周邊，陽極設置於從該突起部先端起離1〇〇 pm的位 與實施例1相同地，在電極5及陽極7之間逐漸施加電 壓，從1.5 kV的電壓起，從ρ型鑽石的突起部檢測到電子 的放出。接著在鑽石LED上施加30 V的電壓使之發光。該 發光中係由數種發光產生，主要之發光是自由激發子發 光，副能帶是能帶A的發光。使LED繼續發光，同時在電 極5及陽極6之間逐漸施加電壓，則從6〇〇 v起可以檢測到 電子的放出，可確認出電子開始放出的臨限值電壓降低。 實施例6 用鑽石粉對石夕晶圓進行損傷處理後，用燈絲 CVD(filament CVD)法合成p型侧摻雜鑽石。合成條件為： 石夕晶圓溫度為800 °C，燈絲溫度為21 〇〇 °c，壓力為丨3 3 kPa曱烧/氫》辰度比為2.0%，在溶解於丙g同之石朋酸三曱酉旨 中通入氬氣泡，使硼/碳濃度比成為〇.1%。將P型硼摻雜鑽 石的厚度合成到20 μηι。該ρ型鑽石除了具有ρ型導電性之 外，由於是多結晶，故包含結晶粒界及差排等缺陷。 接著研磨ρ型删摻雜鑽石的表面，與實施例1相同地形 成點狀的Α1膜，用RIE法蝕刻之，將ρ型硼摻雜鑽石加工成 突起形狀。再將之放入燈絲CVD裝置中，在85(rc下進行 96090.doc -16- 200522122 ίο分鐘的氫電漿處理，對型镨 奵P孓鑽石的表面進行氫終端處 理。再與實施例1相同地用Ti/Au形成歐姆電極。 如圖6所示’另外準備氮化㈣接合的鑽石LED，在 真空室内設置該鑽石LED6〇及陽極7之外，並設置突起形 狀的P型鑽石2。LED設置於上述p型鑽石的突起部周邊， 陽極設置於從該突起部先端起離_μιη的位置。 與實施例1相同地，在電極 电位D及防極7之間逐漸施加電 壓，從1.5 kv的電壓起，你 j ^ 型鑽石的突起部檢測到電子 的放出。使LED繼續發朵，η n士丄 只^先同時在電極5與陽極6之間逐漸 施加電壓，則從500 V起可以 Τ以k測到電子的放出，可確認 出電子開始放出的臨限值電壓降低。 產業上利用性 本發明的鑽石電子放出元株 从, 凡件由具有可激發電子的發光元 件，故與先前技術的電子- 動w m H 出70件相較之下，可用較低驅 動電壓侍到咼電子放出特性， 而可形成小型電子放出元 件。由於係將發光元件及鑽 及鑽石陰極配置於電子搶内部，故 可製侍小型且具有高效率 電子放出特性之電子線源。因 此’使用本發明之電子放ψ 一 ^ 敌出7°件，可提供比先前技術更高 性1b的電子線應用機器 ^ , φ ^ ^ U镟波振盪管、高頻波放大元 件或電子線曝光等電子線加工裝置。 【圖式簡單說明】 ' ° 圖1為本發明的鑽石電 放出70件的剖面示意圖。 圖2為圖1的鑽石電子 一 孜出7L件的能帶圖。 圖3為本發明的另—鑽 电于放出7G件的剖面不意圖。 96090.doc 200522122 圖4為圖3的鑽石電子放出元件的能帶圖。 圖5為本發明的另一鑽石電子放出元件的剖一 圖6為本發明的另一鑽石電子放出元件的咅面不意圖。 圖7為圖6的鑽石電子放出元件的能帶圖、°彳面不意圖。 圖8為先前技術的鑽石電子放出元件的立 【主要元件符號說明】 、°彳面示意圖。 1 硫摻雜鑽石 2 P型鑽石 4 肖特基電極 5 電極 6 電極 7 陽極 8 控制電極 9 絕緣體 10 鑽石單晶 21 傳導帶 22 價電子帶 23 雜質能階 24 雜質能階 25 真空能階 26 起因於缺陷的能階 60 鑽石LED 80 電極 81 n型鑽石 82 Ρ型鑽石200522122 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a diamond electron emitting element that emits electrons and an electron wire source using the diamond electron emitting element. It is widely used for high-frequency amplification, microwave oscillation, and radiation. Components, electron beam exposure devices, etc. [Prior Art] In recent years, in addition to hot cathodes, the development of cold cathode elements using molybdenum or carbon nanotubes has also been underway. In addition, diamond cathodes have attracted attention because of their negative electron affinity. Various forms of diamond cathodes have been published. For example, there are those coated with a diamond on a metal cathode disclosed in, for example, a pn-type junction disclosed in Japanese Patent Publication No. W093 / 15522, or a Journal Off Vac Science and Technology B14 (1996) 2050. As shown in FIG. 8, a pn-type junction is formed on a p-type diamond 82, an n-type diamond 81 is laminated, an electrode 80 is formed thereon, and a bias voltage is applied to emit electrons. Also, it has been proposed that a diamond cathode is formed in a mold of Si as disclosed in Japanese Patent Laid-Open No. 8-264111 or W098 / 44529, and a sharpened diamond cathode is formed. The above-mentioned diamond cathode uses a strong electric field to release electrons into a vacuum, but it is also possible to excite the electrons with light and then release the electrons from the cathode. For example, Japanese Patent Gazette Nos. 10-149761, JP-A, and 2000-357449 propose such techniques. These are all used to measure the emitted electrons as the user of the photodetector. [Summary] The components disclosed in the above patent documents must apply a strong electric field or high operation. 96090.doc 200522122 The electrons radiate fire from the components into a vacuum. And what people are paying attention to—in cold cathodes… strengthen the electric field, and reduce the operating power by setting electrodes on the emitters of multiple =, but if you want to advance:: To improve the operating efficiency and reduce the driving power, you need lower power The purpose of the present invention is to solve the above-mentioned problems, and to make the electron emitting element and source with lower voltage and high efficiency.-The diamond electron emitting element of this month has the ability to irradiate the cathode A light emitting element, and at least the electron emission surface of the cathode is made of diamond. As shown in Figure 4, because it has a light-emitting element, it can excite electrons to the conduction band 21 of a diamond higher than the vacuum level 25 by light, so the voltage of emitted electrons can be greatly reduced, and a low voltage can be obtained. Driven small electronic discharge components. The electron emission surface of the cathode is preferably a diamond diamond semiconductor. The impurity level of the η-type diamond is close to the conduction band, so even if it is excited by light with lower energy, it can excite electrons to the conduction band 'and release electrons, so the efficiency is better. The above-mentioned light-emitting 7L piece is preferably made of diamond. The larger the band gap and the nd gap of the diamond 'can excite electrons with higher energy, so the operating efficiency can be improved. What is the electron emission surface of the above cathode? Diamond semiconductor. Even if a band bend occurs on the surface of the diamond, since the potential of the p-type diamond semiconductor decreases near the surface, electrons excited to the conduction band are easily released. In this case, the P-type diamond semiconductor preferably contains a crystal defect or a postal component. The so-called crystal defects are crystal vacancy defects, impurities, and lattice vacancy pairs caused by 96090.doc 200522122 defects, differential row defects, grain boundaries, twin crystals, and so on. The sp2 component refers to graphite, amorphous carbon, fullerene, and the like. The diamond light emitting element can emit light with high energy such as free exciton emission, and can also emit light with low energy such as band A and the like. If it contains crystal defects or sP2 components, the energy level in the band gap in the diamond will increase, so light with lower energy can be used to excite electrons into the conduction band, which can increase the amount of electrons emitted. The electron emission surface of the cathode is preferably a hydrogen terminal processor. If treated by hydrogen termination, the electron affinity of the diamond surface as the electron emission surface is negative, so the electrons excited to the conduction band can easily be released into vacuum. The electron emission surface of the cathode may be treated with an oxygen termmal. In particular, when the electron emission surface of the cathode is an n-type diamond semiconductor, if the surface is treated with hydrogen termination, holes generated on the surface will reduce electrons as carriers of the cathode, so the cathode has high resistance. If the surface is treated with oxygen termination, this phenomenon does not occur, so a low-resistance cathode can be formed. Moreover, it is preferable that the above-mentioned hair element element is formed by bonding of a diamond to a diamond. The light-emitting element formed by diamond's ρη junction emits short-wavelength light such as 5.27 eV of free exciton, so it is easy to emit electrons. In addition, by using diamond of the same material as the cathode, it is easy to integrally form the light-emitting element and the cathode. In addition, the light-emitting element may be formed by a Schottky junction of a diamond and a metal, or a MIS (Metal Insulator Semiconductor) structure 96090.doc 200522122. Schottky coupling or MIS structure emits light with a shorter wavelength, so it can excite electrons of deeper energy levels, and the energy of the excited electrons is higher, so the probability of electron emission is higher, and it is easier to emit electrons. The electron emission surface of the cathode preferably has a sharp protruding portion. The electric field is concentrated in the front end of the sharp protrusion, so the operating voltage can be reduced. The wavelength energy of the light emitted by the light-emitting element preferably includes 50 to 54. This wavelength is mainly caused by the free excitons of the diamond. If this wavelength is used, electrons can be excited from a lower energy level to the conduction band, and therefore, electrons can be emitted with high efficiency by, for example, exciting from the energy level of boron of a P-type impurity. The wavelength energy of the light emitted by the light-emitting element is preferably 2 () ev or more. Wavelengths above 2.0 eV include defects caused by diamonds, for example, energy band A. If the wavelength of light is above 2.0 eV, the energy levels near the conduction band can be excited, such as doped with n-type nitrogen. The impurity level of the diamond allows the type 11 diamond cathode to emit electrons with high efficiency. The prior art photocathode excites electrons in the valence electron band with light having a larger band gap energy, and the present invention can be excited with light having a smaller band gap energy than a diamond as described above. As such, the light of the luminescent element is preferably one that excites electrons of the impurity level of the diamond to the conduction band. The light of the light-emitting element is preferably one that excites the energy-level electrons in the band gap of the diamond to conduct ▼. Especially when the cathode is a rhodium-type diamond, the light of the emitting element is preferably any of graphite, amorphous carbon, diamond-like carbon, s-lerene, lattice defects, differential row defects, and grain boundary defects in the P-type diamond. One-level electrons are excited to the conduction band. If this excitation is used as the electron beam source, even the light with a wavelength smaller than the energy gap of the diamond here can excite the conduction band and increase the amount of electron emission. 96090.doc 200522122 In the case of diamonds, at least one kind of 亓 |, Xujia 3 helium, phosphorus, sulfur, lithium. If you use these miscellaneous items, it is called excitable π * which contains butterfly as a miscellaneous element: increase the carrier electrons, so you can increase the electrons in the luminescence and increase the electron emission. The light-emitting element is not limited to a III-V semiconductor. — Πτ with lice compound + conductor thousand conductors. For example, the band gap of GaN and CBN can be as wide as 6 3 v. The temple is particularly 疋 6, so the energy of luminescence is high, and the crystal structure is close to that of diamond. Layered structure such as Cheng, Hetroepitaxy and so on. The two or more light emitting elements are preferably those formed with the cathode-body. By using: ', the distance between the electron emission surface and the light-emitting element can be shortened, so the electricity conversion efficiency can be improved, and the electron source using the emission element can be miniaturized. In particular, if a diamond is used as an electrical element, the cathode and the light-emitting element can be easily integrated. Furthermore, the present invention provides an electron source using a diamond electron emitting element, characterized in that a light emitting element that irradiates light to a cathode, and at least a cathode whose electron emitting surface is diamond are disposed inside the electron grab. With this structure, a small electronic wire source capable of being driven at a low voltage can be obtained. In the electron beam source of the present invention, it is preferred that the cathode is provided with at least its electron emitting surface being diamond ', and the anode is disposed across a space, and a positive voltage to the cathode is applied to the anode to act. Furthermore, a control electrode may be provided between the cathode and the anode for controlling an electron current emitted from the cathode. The amount of electrons emitted can be freely controlled using the control electrode. [Embodiment] 96090.doc -10- 200522122 Example 1 Next, the thickness of the n-type sulfur-doped diamond is reduced by the plating method! _ Na. The A1 film was processed into a micro-diameter 5_ dot shape by a micro-film method and a wet-etching method. Thereafter, the sulfur-doped diamond was sulfided by the RIE method, and the sulfur-doped diamond was pulverized into protrusions as shown in FIG. 1. Then thoroughly in the atmosphere. Annealing at 3 ° C for 3 G minutes, so as to counter-sulfur, n-type sulfur-doped diamond was synthesized by microwave plasma CVD method on the ⑽) surface of the • type diamond single crystal synthesized by the high temperature and high dust method. Synthetic conditions are: P-type diamond temperature is ⑽ 'A, hydrogen concentration ratio is 1G%, hydrogen sulfide core concentration ratio is WOO ppm. The thickness of the n-type sulfur-doped diamond was synthesized to 10 ^ claws. The surface of the doped diamond is oxygen terminated. Next, electrodes 5 and 6 are formed on the plane portion of the sulfur-doped diamond and on the surface opposite to the surface of the sulfur-doped diamond forming the p-type diamond 2. The formation method is to implant Ar ions on the surface of the diamond forming the electrode to graphitize the diamond, and then heat it to 3001, and then vapor-deposit Ti / Au to form ohmic electrodes 5 and 6. The diamond having the electrode formed with the protruding portion is placed in a vacuum chamber (not shown) ', and the anode 7 is disposed at a distance of 100 μm from the front end of the protruding portion. First, a voltage is gradually applied between the electrode 5 and the anode 7, and from the kV, the emission of electrons is detected from the protrusion of the n-type diamond. Then, a voltage of 10 ν was applied between the electrodes 5 and 6, and the light emitting hv was confirmed from the ρη bonding layer. The wavelength range of this emission is quite wide, but the free exciton emission with a dominant wavelength of 235 nm and the emission of an energy band A centered at 430 nm. Then, the ρη bonding layer continues to emit light, and at the same time, a voltage is gradually applied between the electrodes 5 and 7, and the electron emission can be detected from 650 V. In this way, it was confirmed that as the light was emitted, the voltage at which electrons started to be emitted decreased. 96090.doc -11-200522122 It can be seen from FIG. 2 that the electrons at the impurity level 23 of the dust diamond 1 are in the η-type load χ; the electrons of the impurity level 23 of the dust diamond 1 are excited to the conduction band 21 which is 咼 than the vacuum energy white 5 with luminescence hv. The threshold voltage at which the electrons start to emit is greatly increased ^ θ & again, the electron emission current detected at the% pole is increased. Example 2 Synthesis of n-type phosphorus-doped diamond i by microwave plasma CVD method on the surface of ㈣-type diamond single crystal ig synthesized by high temperature and high pressure method is as follows: the temperature of chemical diamond is 870 ° C ′ A hospital / hydrogen concentration ratio was 0.05%, and the concentration ratio of lin / methane was W_0Ppm. The thickness of n-type ytterbium-doped diamond is synthesized to ι0㈣. / On the n-type diamond, p-type boron-doped diamond was synthesized by the same microwave plasma CVD method. The synthesis conditions are: the temperature of the Ib diamond is 83 ° C, the methane / hydrogen concentration ratio is 6.0%, and the concentration ratio of the secondary post / methylbenzene concentration is 167 ppm. The thickness of the p-type boron exchange diamond is synthesized to 0 μm. In addition, many p-type boron-doped diamonds have crystal defects such as twins. Next, in the same manner as in Example 1, a dot-shaped A1 film was formed on the P-type diamond, and the p-type diamond was etched by the RIE method. As shown in FIG. 3, the p-type diamond 2 was processed into a shape having protrusions. Then, it was placed in a microwave plasma Cvd device, and then subjected to a holmium plasma treatment at 85 ° C. for 10 minutes, so that the surface of the p-type diamond was hydrogen-terminated. An ohmic electrode 5 λ 6 ° was formed from Ti / Au in the same manner as in Example 丨 and then an anode 7 ° away from 100 μm was provided in a vacuum chamber in the same manner as in Example 1. In the same manner as in Example 1, an electrode 5 and A voltage gradually applied between the anodes 7 starts from 1.5 kV, and the emission of electrons is detected from the protrusion of the p-type diamond. Next, a voltage of 10 V is applied between the electrodes 5 and 6, and the hair-level can be confirmed from the punch joint layer 96090.doc -12-200522122. The wavelength range of this light emission is quite wide, but the free exciton light emission with the dominant wavelength of 235 ° and the light emission of the energy band A widely distributed around 43Gnm center. Then, the pn bonding layer continues to emit light, and at the same time, electric dust is gradually applied between the electrodes 5 and 7, and the electron emission can be detected from _V. In this way, it was confirmed that as the light was emitted, the voltage at which electrons started to be emitted decreased. It can be seen from FIG. 4 that the threshold of the impurity level in the p-type diamond 2 and the energy level 26 due to a defect is excited to a conduction band 2 1 that is higher than the vacuum energy _ and the threshold at which the electrons start to emit The value of electricity is greatly reduced. At this time, the electron emission current detected at the anode is increased. Example 3 On the (100) surface of several diamond single crystals 10 synthesized by the high temperature and high pressure method, a microwave plasma was used. The doped diamond i was synthesized by CVD method. The synthetic conditions are: the temperature of the diamond is 830 ° C, the methane / hydrogen concentration ratio is 60%, and the diborane / methane concentration ratio is 167Ppm. The thickness of the p-type boron-doped diamond After synthesizing to i0, a dot-shaped ai film was formed on the? -Type diamond i in the same manner as in Example 1. The p-type diamond was etched by the RIE method. The ohmic electrode 5 was again formed of Ti / Au in the same manner as in the embodiment. Then, W was vapor-deposited around the protrusions to form a Schottky electrode 4. Insulators 9 and Mo made of SiO 2 were deposited on the outer periphery of the boron-doped diamond to form a control electrode 8. Next, in the same manner as in Example 1, an anode 7 at a distance of 100 μm was provided in the vacuum chamber. As in Example 1, a voltage was gradually applied between the electrodes 5 and the anode 7 and between the electrodes 5 and 8, respectively, from 1 kV and 300 V. From the voltage of 960, electron emission was detected from the protrusion of the p-shaped drill 96090.doc -13- 200522122 stone. Then, a voltage of 10 V was applied between the electrodes 5 and 4, and the light emitting hv was confirmed from the Schottky bonding layer. The wavelength of this light emission includes a wide range from free exciton light emission to energy band A light emission. Then, the Schottky bonding layer continues to emit light, and at the same time, a voltage is gradually applied between the electrodes 5 and 7, and the electron emission can be detected from 600 V. In this way, it can be confirmed that with the emission of light, electrons at the impurity level of the p-type diamond are excited to a conduction band higher than the vacuum level, and the threshold voltage at which the electrons start emitting is greatly reduced. At this time, the electron emission current detected at the anode increases. When the voltage applied between the electrodes 5 and 8 is changed, the electron emission current changes linearly. Furthermore, even if the amount of light emitted is changed by changing the voltage applied between the electrodes 5 and 4, the amount of light emitted by the electron emission current increases proportionally. Example 4 In the same manner as in Example 3, a p-type boron-doped diamond 2 having a thickness of 1 μm was synthesized on the (100) plane of the ib-type diamond single crystal 10. As shown in Fig. 6, the p-type diamond is processed into a shape having a protruding portion. After performing hydrogen termination treatment on the surface of the p-type diamond in the same manner as in Example 2, an ohmic electrode 5 was formed using Ti / Au. In addition, a pn-bonded drill D composed of boron-doped diamond and boron-doped diamond is prepared to place the diamond LED 60 and the anode 7 in a vacuum to the inside 5. The iron stone LED is provided around the protrusion of the p-type diamond, and the anode is provided at a position of 100 μm from the tip of the protrusion. As in Example 1, a voltage was gradually applied between the electrode 5 and the anode 7, and from a voltage of 丨 kV, the discharge of electricity was detected from the protrusion of the rhodium-type diamond 96090.doc -14-200522122. A voltage of 30 V was then applied to the diamond LED to make it glow. This luminescence is generated by several kinds of luminescence, the main luminescence is the emission of free exciton, and the sub-band is the luminescence of energy band A. Then let the LED continue to emit light, and at the same time gradually apply a voltage between the electrode 5 and the anode 6, the electron emission can be detected from 650 V, and it can be confirmed that the threshold voltage at which the electron starts emitting is reduced. 0 Figure 7 shows a diamond Band diagram. 21 is a conduction band and 22 is a valence band. With the free exciton emission of 5.27 eV, the electrons at the impurity level 24 of the p-type diamond are excited to a conduction band higher than the vacuum level 25. The hydrogen-terminated surface has negative electron affinity, so Easily emit electrons. If the amount of light emitted by the LED is changed, the electron emission current will change linearly. Example 5 After the silicon wafer was damaged with diamond powder, p-type boron-doped diamond was synthesized by filament CVD (filament CVD). The synthesis conditions are: the silicon wafer temperature is 800 ° C, the filament temperature is 2100 ° c, the pressure is 13 3 kpa, and the concentration ratio of oxane / hydrogen is 2.0%. The argon bubbles were adjusted to a boron / carbon concentration ratio of 0.1%. will? The thickness of the type-doped diamond is synthesized to 20 μm. What rho diamonds have? Since it is polycrystalline, it includes defects such as crystal grain boundaries and differential discharge. Next, the surface of the! ≫ -type boron-doped diamond was ground in the same manner as in the Example ", and the doped diamond was processed into a protruding shape. Then put it into the filament CVD device, and treat the p-type diamond with a hydrogen plasma treatment at a temperature of 850 to 10 minutes. The diamond surface is hydrogen terminated at 96090.doc 15 200522122. In the same manner as in Example 1, an ohmic electrode was made of Ti / AUB. As shown in Fig. 6, a diamond-bonded diamond LED was prepared separately in the same manner as in Example 4, and the diamond LED 60 and the anode 7 were provided in a vacuum chamber, and a p-type diamond 2 having a protruding shape was provided. The diamond LED is provided around the protruding portion of the p-type diamond, and the anode is provided at a position 100 pm from the tip of the protruding portion. As in Example 1, a voltage is gradually applied between the electrode 5 and the anode 7 from 1.5. From a voltage of kV, the emission of electrons is detected from the protrusion of the rhodium-type diamond. A voltage of 30 V was then applied to the diamond LED to make it glow. The light emission is generated by several kinds of light emission. The main light emission is the free exciton light emission, and the side energy band is the light emission of the energy band A. When the LED continues to emit light, and a voltage is gradually applied between the electrode 5 and the anode 6, the emission of electrons can be detected from 600V, and it can be confirmed that the threshold voltage at which the electrons start emitting is reduced. Example 6 After the Shi Xi wafer was damaged with diamond powder, a p-side doped diamond was synthesized by filament CVD (filament CVD). The synthesis conditions are as follows: the temperature of Shi Xi's wafer is 800 ° C, the filament temperature is 2100 ° C, the pressure is 丨 3 3 kPa, and the temperature ratio is 2.0%. An argon bubble was introduced into the acid trioxide, so that the boron / carbon concentration ratio became 0.1%. The thickness of the P-type boron doped diamond was synthesized to 20 μm. In addition to the p-type conductivity, this rhodium-type diamond is polycrystalline, and therefore includes defects such as crystal grain boundaries and differential rows. Next, the surface of the p-type doped diamond was ground, and a spot-shaped A1 film formed in the same manner as in Example 1 was etched by the RIE method to process the p-type boron-doped diamond into a protrusion shape. Then put it into a filament CVD apparatus, and perform a hydrogen plasma treatment at 85 ° C (96090.doc -16- 200522122) for one minute to perform hydrogen termination treatment on the surface of the type 镨 奵 P 孓 diamond. The same procedure as in Example 1 Similarly, an ohmic electrode was formed using Ti / Au. As shown in FIG. 6, a diamond LED bonded with osmium nitride was prepared separately. The diamond LED 60 and the anode 7 were placed in a vacuum chamber, and a P-shaped diamond 2 having a protruding shape was provided. The LED is provided around the protrusion of the p-type diamond, and the anode is provided at a position separated from the tip of the protrusion by _μιη. As in Example 1, a voltage is gradually applied between the electrode potential D and the guard electrode 7 from 1.5. From the voltage of kv, the projection of your j ^ type diamond detects the release of electrons. Let the LED continue to bloom, η n 丄 only apply voltage gradually between the electrode 5 and the anode 6 at the same time, then from 500 V The emission of electrons can be measured at TK, and it can be confirmed that the threshold voltage at which the electrons start to emit is reduced. Industrial Applicability The diamond electron emission element of the present invention is composed of light emitting elements that can excite electrons. Prior art electronics-dynamic wm H Compared with 70 pieces, it can use a lower driving voltage to serve the plutonium electron emission characteristics, and can form a small electron emission element. Since the light emitting element and the diamond and diamond cathode are arranged inside the electron grab, it can be made small and An electron beam source with high-efficiency electron emission characteristics. Therefore, 'Using the electron beam of the present invention ψ 1 ^ enemy 7 ° pieces, can provide electronic wire application equipment 1b higher than the previous technology ^, φ ^ ^ U 镟 波Oscillating tube, high-frequency wave amplifying element or electron wire exposure and other electronic wire processing devices. [Brief description of the drawings] 'Figure 1 is a schematic cross-sectional view of 70 diamond electric discharges of the present invention. Band diagram of 7L piece. Figure 3 is another part of the present invention—the cross section of 7G is not intended to be drilled. 96090.doc 200522122 Figure 4 is a band diagram of the diamond electron emitting component of Figure 3. Figure 5 is the invention Sectional view of another diamond electron emission element of FIG. 6 is a schematic view of a diamond electron emission element of the present invention. FIG. 7 is a band diagram of the diamond electron emission element of FIG. 8 is the prior art Dimensions of diamond electronic discharge components [Description of main component symbols], Schematic diagram of surface. 1 Sulfur doped diamond 2 P-type diamond 4 Schottky electrode 5 Electrode 6 Electrode 7 Anode 8 Control electrode 9 Insulator 10 Diamond single crystal 21 Conduction Band 22 Valence electron band 23 Impurity level 24 Impurity level 25 Vacuum level 26 Energy level due to defects 60 Diamond LED 80 Electrode 81 n-type diamond 82 P-type diamond
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